Phenolaldimines as froth flotation reagents

ABSTRACT

A froth flotation method for the recovery of iron, cobalt, nickel, copper, and vanadium minerals from their ores over silica, alumino, and ferromagnesian silicates, which comprises subjecting the comminuted ore of aforesaid metals to froth flotation process in the presence of an effective amount of phenolaldimines; the indicated compounds provide selectivity and recovery of metal values of iron, cobalt, nickel, copper, and vanadium from their oxide, silicate, sulfide, arsenide, and antimonide ores in an enriched froth concentrate.

llrted States Patent 1 [11] 3,

Petrovich Dec. 23, 1975 PHENOLALDIMINES AS FROTH 3,425,549 2/1969 Dickson 209/166 FLOTATION REAGENTS 3,819,048 6/1974 Weimer 209/166 [76] Inventor: Vojislav Petrovich, 1925 W. Schiller St" Chicago, [IL 60622 Przmary ExammerRobert Halper [22] Filed: Apr. 30, 1974 US. Cl. 209/ 166 [51] Int. Cl. 803D l/02 [58] Field of Search 209/ 166, 167

[56] References Cited UNITED STATES PATENTS 2,272,489 9/1942 Ulrich 260/239 2,296,226 9/1942 Ulrich 260/239 E 2,414,199 l/1947 Gutzeit 209/166 3,056,498 10/1962 DeGroote 209/166 [57] ABSTRACT A froth flotation method for the recovery of iron, cobalt, nickel, copper, and vanadium minerals from their ores over silica, alumino, and ferromagnesian silicates, which comprises subjecting the comminuted ore of aforesaid metals to froth flotation process in the presence of an effective amount of phenolaldimines; the indicated compounds provide selectivity and recovery of metal values of iron, cobalt, nickel, copper, and vanadium from their oxide, silicate, sulfide, arsenide, and antimonide ores in an enriched froth concentrate.

5 Claims, N0 Drawings PHENOLALDIMINES AS FROTH FLOTATION REAGENTS This invention relates to the concentration of metal values from their ores. Particularly, it relates to the use of aryl hydroxyaldimines as flotation agents to effect a separation of metal values in ores from gangue. More particularly, it relates to the use of phenolaldimines as froth flotation reagents for oxide ores of iron; oxide, silicate, and sulfide ores of copper; oxide, silicate, sulfide, arsenide and antimonide ores of cobalt and nickel; and vanadate of heavy metals.

The special feature of this invention using phenolaldimines is in the nonfloating of minerals with divalent iron, the common sulfide of iron as is pyrite, arsenopyrite; furthermore, ferromagnesian silicates and the like minerals, as is garnet, biotite, chlorite, and the like minerals.

THE PREFERRED EMBODIMENTS The preferred embodiments of collectors of this invention are as follows:

Cresylaldimine adduct of cresylic acid of the formula:

Cresylaldimine adduct of primary alcohol of the formula:

wherein n is an integer from 5 to 15.

Cresylaldimine adduct of polyehylene glycol of the formula:

di-Hydroxyterephthalic-mono-aldimine:

HO H moo-O H Terephthalic-monohydroxyaldimine adduct of polyethylene glycol in which compounds n is an integer from In said froth flotation reagents the collecting groups function through the conjunctive action of phenolic hydroxide and aldimine group, i.e. imine group =NH attached to a residue of aldehyde, both groups are in beta position to each other. The active group of this constitution, i.e., of a phenolic hydroxide and an aldimine are the only promoting groups and essential part of the flotation reagent with collecting power. All other grouping parts, i.e., the alcoholic hydrocarbon group, the adduct of cresylic acid are auxiliar groupings which aid in the bubbles formation, an essentially secondary property.

The active groups are hydrophilic until promoting takes place and aids in solubility of the reagents. After promoting, the hydrophilic property of the active group is lost, in which case the hydrophilic part outside the active group begins to form bubbles due to its constitution. Thus, these reagents function as complete froth flotation collector-frothers.

Good recoveries of said metal values in respective minerals are obtained if the reagents of the present invention are used in a circuit having a pH about 8 to 12.

Further advantage of this invention resides in the fact that no specific frothing agents are to be employed, since the products of the present invention develop sufficient froth to be a good promoter and frother at the same time, which adds in the over-all economy and operativity of the process.

The further advantage of this invention resides in the feasibility of recycling the processed water after desliming by cycloning, which would enable big savings in alkalies and ammonia.

A further object of this invention is to provide flotation agents with collecting and frothing properties for collecting iron oxide ores, copper oxide, silicate, and sulfide ores, nickel as well as cobalt oxide, silicate, sulfide, arsenide, and antimonide ores, and a vanadate of heavy metals.

A still further object is to disclose novel agents for handling ores wherein the use of activation step of any kind is unnecessary. l have discovered that most gangue minerals are unaffected by the collector-frothers of this invention. Hence a method for obtaining a highly selective concentration of the desired metal values is provided.

The collector-frothers of this invention, which func-' tion by chemical reaction with the ore have complexing and presumably chelating ability at the very surface of mineral or portion of surface of the mineral particle of the ore treated. It is obvious that the polar part, i.e., the complexing or chelating groups, i.e., phenolic-hydroxyl and aldehyde-imine group of the reagent are oriented inwards the ore particle, while the hydroxy-hydrocarbon part is oriented outward from said particle, Thus the attachment of these organic complexing and chelating ingredients to the ore particles form a water repellent surface, or barrier, around at least a part of the surface of the ore particle and thereby facilitates the formation of the froth when the ore slurry is agitated in the presence of air.

' The froth flotation of the present invention is carried out in accordance with good flotation practice and usually, though not always, involves flotation in rougher cells, followed by one or several cleanings of the rougher concentrate. The reagents awe effective in small amounts and the promotion is sufficiently persis- 3 tent so that it is feasible to carry out the rougher and cleaner flotation with a single addition of the reagents at the beginning of the operation. On the other hand, it is sometimes advantageous to use stage additions of 4 nipulation as follows: for the red hematite, copper sulfide, and nickel silicate the feed was sized to pass 100 mesh standard sieve. Transferring the sized flotation feed in the flotation machine, various amounts of said reagents. Pulp densities are in general the same as in substituted phenolaldimines for collecting purposes other applications of froth flotation practice, i.e., about were added. After this step. the pulp of mineral slurry l5 to 30 percent of solids by weight. was conditioned for five minutes, The amounts of col- The flotation plant practice applying the inventors lector are indicated in the accompanying table. Before method by serving the substituted phenolaldimines for skimming of the rougher concentrate the pulp of minthe recovery of metal values, floating the hereinbefore ll) eral slurry was conditioned and aerated for three to five said ores and minerals of iron, cobalt, nickel, copper, minutes. The rougher concentrates were skimmed from and vanadium with phenolaldimines having collecting about five to ten minutes and afterwards cleaned with and frothing properties, the ore is crushed, milled and processed water. sized to at least 80 to 120 standard mesh sieve, which The flotation test of sized sample was accomplished depends on the particular ore treated. Milling to finer in a 50 grams cell for ullmannite and chloantite for sizes is preferable. The crushed and sized ore is pulped determination of floatability of nickel ores; and smaltand as a mineral slurry is ready for treatment in the ite and linnalite for determination of floatability of flotation plant equipment, i.e. by passing through the cobalt ores; as well as carnotite for determination of conditioner where the collector is added. From the floatability of vanadium ores, i.e., with 5 grams of a conditioner the pulp is pumped in the receiving box of mixture of ullmannite and chloantite, or a mixture of the first stage or the main flotation bank. In the main smaltite and linnalite, and grams of a mixture of flotation bank the froth produced by agitation and pyrite, arsenopyrite, pyrrhotite and galena, as well as aeration is skimmed or is overflowing in the usual man- 45 grams of a mixture of crystalline schist material and ner. ln most cases it is advantageous to use multiple sandstone as gangue material with 5 grams ofcarnotite. stage flotation process to treat the underflow or par- 25 The addition of reagents was done dropwise. The retially metal value barren pulp to increase the degree of covery of ullmannite-chloantite; smaltite-linnaeite; and separation or to enhance the grade of recovery, Also, carnotite was obtained by microscopic count.

Ore Collector Assay of products treated pound per ton Feed Cone. Recovery Example 1 Phthalic-mono-hydroxyaldimine Fe 71 Fe 7( Fe 7r adduct of octylene glycol Hematite 0.6 282 64.1 92.3

Example 2 Cresylaldiminooctanol Ni 7: Ni 71 Ni 71 Garnierite Ni-silicate 0.15 2.32 l3.6 89.4

Example 3 Cresylaldimine adduct of Cu 7: Cu Cu 71 Copper cresylic acid sulfide 0.25 2.12 26.2 94.2

Example 4 di-Hydroxyphthalic-mono- Cu 7: Cu 7( Cu 7r Copper -aldimine sulfide 0.25 2.10 26.0 95.l

Example 5 Phthalic-mono-hydroxyaldimine 90.0 Ullmannite adduct of octylene glycol by microscopic count Chloanthite Example 6 Cresylaldimine adduct of 84.0 Smaltite cresylic acid by microscopic count linnalite Example 7 Cresylaldimine adduct of 88.0 J Carnotite octylene glycol by microscopic count the use of varying amounts of emulsifiers, disperssant, It is to be understood that the foregoing detailed and depressants etc. in different stages may be used to discussion is for the purpose of illustration only, and it advantage to obtain the highest yield and best separais not intended as being limiting to the spirit or scope of tion. the appended claims.

Having disclosed the novel collector-frothers of this What I claim: invention as well as the handling of the mineral slurry, l. A method of beneficiating ores selected from the I have to say the final object of this invention is to group consisting of oxide of iron, oxide, silicate, sulprovide a method for the flotation recovery of minerals fide, arsenide, and antimonide of copper, nickel, and containing iron, cobalt, nickel, copper, and vanadium. cobalt, the vanadates of heavy metals by froth flotation The above discussion as well as the disclosure illusprocess to produce a froth concentrate of desired metal trate my invention in a broad and general way; for a value, which comprises; effecting froth flotation of detailed illustration thereof the examples of the preaforesaid ores in the presence of cresylaldimine adduct ferred embodiments of flotation practice are set forth below.

The procedure in performing the laboratory examples for iron, nickel, copper, ores was of the same maof cresylic acid as collector in a pulp of mineral slurry having a pH of 8 to 12; and recovering the desired metal value in an enriched froth concentrate, leaving a tailings poor in the desired metal value.

2. A method of beneficiating ores selected from the group consisting of oxide of iron, oxide, silicate, sulfide, arsenide, and antimonide of copper, nickel, and cobalt, the vanadates of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises: effecting froth flotation of aforesaid ores in the presence of cresylaldimine adduct of primary alcohol as collector, said adducts have from 5 to methyl groups in said primary alcohol; the flotation being effected in a pulp of mineral slurry having a pH of 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal value.

3. A method of beneficiating ores selected from the group consisting of oxide of iron, oxide, silicate, sulfide, arsenide, and antimonide of copper, nickel, and cobalt, the vanadates of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises; effecting froth flotation of aforesaid ores in the presence of cresylaldimine adduct of polyethylene glycol as collector, said adducts have from 5 to 15 methyl groups in said polyethylene glycol, the flotation being effected in a pulp of mineral slurry having a pH from 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal value.

4. A method of beneflciating ores selected from the group consisting of oxide or iron, oxide, silicate, sulfide, arsenide, and antimonide of copper, nickel, and cobalt, the vanadates of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises: effecting froth flotation of aforesaid ores in the presence of di-hydroxyterephthalic-mono-aldimine as collector in a pulp of mineral slurry having a pH from 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal value.

5. A method of beneficiating ores selected from the group consisting of oxide of iron, oxide, silicate, sulfide arsenide, and antimonide of copper, nickel, and cobalt, the vanadate of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises: effecting froth flotation of aforesaid ores in the presence of terephthalic-mono-hydroxyaldimine adduct of polyethylene glycol as collector, said adducts have from 5 to 15 methyl groups in said polyethylene glycol, the flotation being effected in a pulp of mineral slurry having a pH from 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal 

1. A METHOD OF BENEFICIATION ORES SELECTED FROM THE GROUP CONSISTING OF OXIDE OF IRON, OXIDE, SILICATE, SULFIDE, ARSENIDE, AND ANTIMONIDE OF COPPER, NICKEL, AND COBALT, THE VENADATES OF HEAVY METALS BY FROTH FLOTATION PROCESS TO PRODUCE A FROTH CONCENTRATION OF DESIRED METAL VALUE, WHICH COMPRISES; EFFECTING FROTH FLOTATION OF AFORESAID ORES IN THE PRESENCE OF CRESYLALDIMINE ADDUCT OF CRESYLIC ACID AS COLLECTOR IN A PULP OF MINERAL SLURRY HAVING A PH OF 8 TO 12; AND RECOVERING THE DESIRED METAL VALUE IN AN ENRICHED FROTH CONCENTRATE, LEAVING A TAILINGS POOR IN THE DESIRED METAL VALUE.
 2. A method of beneficiating ores selected from the group consisting of oxide of iron, oxide, silicate, sulfide, arsenide, and antimonide of copper, nickel, and cobalt, the vanadates of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises: effecting froth Flotation of aforesaid ores in the presence of cresylaldimine adduct of primary alcohol as collector, said adducts have from 5 to 15 methyl groups in said primary alcohol; the flotation being effected in a pulp of mineral slurry having a pH of 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal value.
 3. A method of beneficiating ores selected from the group consisting of oxide of iron, oxide, silicate, sulfide, arsenide, and antimonide of copper, nickel, and cobalt, the vanadates of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises; effecting froth flotation of aforesaid ores in the presence of cresylaldimine adduct of polyethylene glycol as collector, said adducts have from 5 to 15 methyl groups in said polyethylene glycol, the flotation being effected in a pulp of mineral slurry having a pH from 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal value.
 4. A method of beneficiating ores selected from the group consisting of oxide or iron, oxide, silicate, sulfide, arsenide, and antimonide of copper, nickel, and cobalt, the vanadates of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises: effecting froth flotation of aforesaid ores in the presence of di-hydroxyterephthalic-mono-aldimine as collector in a pulp of mineral slurry having a pH from 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal value.
 5. A method of beneficiating ores selected from the group consisting of oxide of iron, oxide, silicate, sulfide arsenide, and antimonide of copper, nickel, and cobalt, the vanadate of heavy metals by froth flotation process to produce a froth concentrate of desired metal value, which comprises: effecting froth flotation of aforesaid ores in the presence of terephthalic-mono-hydroxyaldimine adduct of polyethylene glycol as collector, said adducts have from 5 to 15 methyl groups in said polyethylene glycol, the flotation being effected in a pulp of mineral slurry having a pH from 8 to 12; and recovering the desired metal value in an enriched froth concentrate leaving a tailings poor in the desired metal value. 